Apparatus for Sensing Environmental Moisture Changes

ABSTRACT

A sensor comprises: an electrically comprises a switchable polymeric element. The polymeric element has at least a first electrical state and a second electrical state and is switchable between the first and second electrical states as a function of predefined environmental changes. The sensor comprises a polymeric matrix and a plurality of conductive particles embedded in the polymeric matrix.

FIELD OF THE INVENTION

The invention relates to sensing apparatus sensitive to environmentalchanges. The invention relates particularly to sensing apparatussensitive to changes in the moisture level of the environment of theapparatus.

BACKGROUND OF THE INVENTION

Sensing systems are pervasive in the world today. Feedback systems withdedicated sensor and processor loops provide indications of speed,acceleration, temperature, mechanical state and a host of other piecesof information. These systems typical require expensive hardwareelements to achieve their performance. There is an unmet need forsensors which may be incorporated into systems at a low cost in order toenable the provision of desired information in everyday situations forimproving the daily lives of consumers. One distinct advantage of thecurrent world in the availability of smartphones which may also serve assensor interrogation devices via capabilities built into the device suchas near field communications, RFID, Bluetooth, WiFi and othercommunications protocols which enable the devices to seek out thecurrent state of properly configured sensors. What is needed are simple,low-cost, environmental sensors which may be remotely interrogated.

SUMMARY OF THE INVENTION

A sensor comprises: a switchable polymeric element. The polymericelement has at least a first electrical state and a second electricalstate and is switchable between the first and second electrical statesas a function of predefined environmental changes. The sensor comprisesa polymeric matrix and a plurality of conductive particulates embeddedin the polymeric matrix.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a schematic illustration of an embodiment of theinvention.

FIG. 2 provides a schematic illustration of an embodiment of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

The following text sets forth a broad description of numerous differentembodiments of the present invention. The description is to be construedas exemplary only and does not describe every possible embodiment sincedescribing every possible embodiment would be impractical, if notimpossible, and it will be understood that any feature, characteristic,component, composition, ingredient, product, step or methodologydescribed herein can be deleted, combined with or substituted for, inwhole or part, any other feature, characteristic, component,composition, ingredient, product, step or methodology described herein.Numerous alternative embodiments could be implemented, using eithercurrent technology or technology developed after the filing date of thispatent, which would still fall within the scope of the claims. It shouldalso be understood that, unless a term is expressly defined in thispatent using the sentence “As used herein, the term ‘______’ is herebydefined to mean . . . ” or a similar sentence, there is no intent tolimit the meaning of that term, either expressly or by implication,beyond its plain or ordinary meaning, and such term should not beinterpreted to be limited in scope based on any statement made in anysection of this patent (other than the language of the claims). No termis intended to be essential to the present invention unless so stated.To the extent that any term recited in the claims at the end of thispatent is referred to in this patent in a manner consistent with asingle meaning, that is done for sake of clarity only so as to notconfuse the reader, and it is not intended that such claim term belimited, by implication or otherwise, to that single meaning. Finally,unless a claim element is defined by reciting the word “means” and afunction without the recital of any structure, it is not intended thatthe scope of any claim element be interpreted based on the applicationof 35 U.S.C. §112, sixth paragraph.

A “chip” as described herein, may be supplanted by a chipless RFIDelement as is known in the art. An LC resonant RF tag, or amultiresonator element may be used in place of the chip in the describedembodiments.

In one aspect, a sensor system comprises an analog-to-digital converterand sensor. The sensor is adapted to provide an output analogous to achange in pH of the environment of the sensor. The analog-to-digitalconverter is adapted to convert an analog output of the sensor to adigital value. The analog-to-digital value is adapted to convert ananalog output of the sensor to a digital value.

The analog to digital converter includes input and output terminals. Theinput terminals of the analog-to-digital converter are disposed inelectrical communication with the output terminals of the sensor.

In one aspect, a sensor system comprises a tag. The tag may comprise oneor more layers of conductive inks and non-conductive inks printed upon asubstrate. Exemplary substrate materials include: polymer films, paper,high permittivity dielectric materials, and FR-4 material. Multiplelayer structures may further comprise partial layers of non-conductingmaterial separating at least portions of the conductive layers.Exemplary conductive layers include copper and silver inks.

The tag comprises at least one radio-frequency chip, a first antennadisposed as a circuit upon a card, coin, or inlay. Exemplary chip/firstantenna combinations include model numbers: RI-I03-112A-03 (13.56 MHz),and RI-INL-R9QM (134.2 kHz), or model TRF7970A, each available fromTexas Instruments, Dallas, Tex. The antenna may be in the physical formof a coil or a dipole, or may comprise a conductive component of aproduct or package in electrical communication with the remainder of thetag. The chip/first antenna combination may be integrated into a unittag available from Kovio, San Jose, Calif. The tag further comprises aconductive polymeric system in electrical communication with the chipand the antenna. The needed power supply for the tag may be provided bythe harvested energy of the RFID circuit because the needed current isin the micro ampere range. The harvested power may be stored with anelement such as a capacitor for use by the tag at a later time.

In one embodiment, a sensor system comprises: a communications elementand a switch. The switch may be configured to enable or disable thecommunications element. The switch comprises a switchable polymericelement. The polymeric element has at least a first electrical state anda second electrical state and is switchable between the first and secondelectrical states as a function of predefined environmental changes. Theswitch may enable or disable the functional capacity of thecommunications element of the system as or after the environmentalchange occurs. Exemplary environmental changes include: wetness,humidity, pH, mechanical strain, solvent compatibility, and combinationsthereof.

The respective sensor elements generally function by having anelectrical state which changes in response to the swelling of a sensorpolymer component in response to selective changes in the environment ofthe sensor.

The humidity sensor may comprise a polyelectrolyte coating. When dry thepolyelectrolyte smart coating has a resistance in the mega-ohms range(open circuit) and less than 3 kilo-ohms when insulted by theenvironment (closed circuit). When insulted by water (deionized) orhumidity, the polymer swells with water thus solubilizing theelectrolyte. In an un-insulted, un-swollen state, the embeddedelectrolyte provides an RF energy pathway to turn on the antennaenabling the RFID to transmit. In one embodiment, the smart coatingformulation enables this transition at about 10 to 15 seconds afterbeing insulted. The embedded electrolyte enhances the hygroscopic natureof this smart coating effectively making it sensitive to humidity. Thewetness, pH, and mechanical strain sensor may comprise conductive fillerelements enmeshed in a non-conductive polymer matrix. As the sensor isexposed to wetness or humidity, the polymer swells as it takes up waterfrom the environment. The swelling polymer matrix reduces theconductivity of the sensor element by increasing the spacing between thediscrete conductive filler particles. As this spacing increases, thepathway for conducting current through the filler of the sensordecreases and may become completely open as and after the swellingleaves no complete conductive pathway through the matrix via the filler

The swelling continuum may be controlled by a pre-determined level ofchemical and/or physical cross-linking. Chemical cross-linking can beinduced thermally, via initiator, via UV, via photo, to name a few.Physical cross-linking can induced be from entanglements, freeze-thawcycles, and crystallization, to name a few. The predeterminedcross-linking level provides an equilibrium swell within the conductiveregion of the swelling region from water or humidity only. Cross-linkingalso serves as a way to amplify the effects of the pH sensitivity. Inthe cross-linked system, changes in pH cause the sensor swell or shrinkin a pre-determined dynamic range.

Prior to the insult, the sensor comprises a conductive pathwaycomprising of a series of discrete particles of conductive material inphysical contact with each other. The conductive pathway provides a pathfor current to flow as part of a circuit into which the sensor has beenincorporated, or in an alternative, the conductive pathway may provide aknown resistance as part of a circuit. As the sensor is exposed to theenvironmental insult, the conductivity of the sensor will fall as theswelling of the polymer matrix increases the distance between discreteconductive particles and may drop to zero in the event that the swellingcreates complete separation of the conductive particles at anycross-section of the previously conductive pathway. The changes inconductivity may be correlated to environmental pH.

The chemiresistor wetness-sensitive smart coating has a resistance inthe low ohms range when dry, enabling conductivity, and the highmega-ohm range when insulted by the environment to cause very lowconductivity. When the smart coating is insulted with water basedliquid, the polymer begins to swell. This swelling induces a percolationthreshold where the volume of the polymer increases to 20-40% of its dryvolume. In doing so, the conductive filler reaches a point where it nolonger can conduct the RF energy between the anode and the cathode sideof open circuit or between two IC leads. In one embodiment, thechemiresistor smart coating formation enables this transition about 5seconds after being insulted. To better disperse the filler, a non-ionicsurfactant Triton X-100 is used.

A chemical-sensitive sensor may be created which is selective to exampletarget chemicals with a Hildebrand solubility parameter within 2× ofpolyethylene co-vinyl acetate. Being insoluble in water, this systemillustrates selective chemical testing in an aqueous environment. Thechemiresistor in the wetness sensing was composed of a water solublepolymer: [poly(vinyl alcohol), M_(w)=89,000-98,000] and conductivefiller (silver coated copper). For the chemical/biosensor, thechemiresistor's polymer can be substituted by another that has a similarsolubility parameter as the target (specifically the HildebrandParameter).

When the selected polymer comes in contact with the analyte of interest,the polymer swells behind the conductive fillers' percolation thresholdwhere the filler does not have sufficient contact to maintainconductivity.

The chemiresistor can be further modified to respond only toenvironments in a pre-determined pH range. The model polymer system maybe intended for enteric coatings. Such coatings are by design made towithstand low pH in the stomach and as they pass through higher pHenvironments in the intestines, the polymer swells/dissolves to releasemedicine. In our case, for a basic pH sensor, we are interested in thesystem swelling past a certain pH threshold causing the filler to pass aconductive percolation threshold. This polymeric system is fundamentallyan aqueous dispersion of proprietary anionic polymers functionalizedwith methacrylic acid. The system may be tailored to dissolve at a pH of5.5. In one embodiment, the sensor may be configured to provide anindication of the pH of the environment. In such an embodiment, thevolumetric changes of the polymer matrix according to the pH of theenvironment may be used to provide the indication of pH. The matrix maybe configured such that there is a known volumetric change via swellingdue to exposure to an aqueous environment, where the matrix responds tothe environment by taking up water and swelling. The matrix may beinduced to a further volumetric change by exposure to an acidic oralkaline environment relative to the pK_(a) of the polymeric matrix. Thepolymer may be configured to respond to a pH increase by swellingfurther due to de-protonation of the acidic matrix in response to a pHin excess of the pK_(a) of a polymeric matrix constituent component. Abasic matrix may alternatively be configured to undergo protonation inresponse to a rising pH and undergo volumetric shrinkage.

The polymeric matrix may also be configured to respond across a range ofpH values by undergoing both a volumetric shrinkage in a first part of arange and a volumetric increase in a second portion of the range. As anexample, a polymeric matrix containing both acidic and basic componentsmay be configured to shrink in volume as the environmental pH rises pastthe pK_(a) of a constituent of the matrix from protonation of thatacidic constituent and at a predetermined pH threshold, the basic secondconstituent to undergo de-protonation to cause the matrix volume toswell.

The matrix may be formulated such that it will respond to a falling pH.In one embodiment, the matrix may swell due to de-protonation as the pHof the environment falls. In an alternative, the matrix may shrink asthe pH falls due to protonation of the matrix.

In one embodiment, the polymeric matrix undergoes a volumetrichysteresis associated with exposure to environmental changes ofparticular pH values. In such an embodiment, the polymeric matrix mayundergo a volumetric change in response to a change in environmental pHand subsequently, undergo a reversal of that volumetric change inresponse to a reversal of the environmental pH. The hysteresis may notbe completely symmetrical in that the final matrix volume at aparticular pH may not precisely mirror the original state of matrixvolume and pH. This incomplete hysteresis symmetry may provide anindication that an environmental event of interest has occurred as thealteration of the matrix volume of the sensor over the course of theevent may yield a sensor having differing electrical characteristicsthan a sensor which has not undergone the insult.

In one embodiment, the polymeric matrix will transition from a firstelectrical state to a second electrical state when insulted by asolution having a pH in the range of interest.

Subsequent to the insult, the matrix may be dried yielding a thirdelectrical state. The third state after drying corresponds to theinsulted state as a function of predefined environmental pH changes, butis not electrically equivalent to the second state. Without being boundby theory, the change in electrical resistance in the third staterelative to the first or second states relates to a combination ofbroken bonds from polymer network strain, salt retention, andre-organization of filler orientation as a function of pH and swelling.

In one embodiment, the polymeric matrix will transition from a firstelectrical state to a second electrical state when insulted by moistureor humidity. Subsequent to the insult, the matrix may be dried yieldinga third electrical state. The third state after drying corresponds tothe initial state as a function of moisture content, but is notelectrically equivalent to the first state.

The polymeric strain sensor from a material standpoint is very similarto the chemiresistor. An elastic polymer is substituted for theenvironmental sensitive polymer. As the polymer elongates from strain,crystalline structures and physical entanglements change orientationthus changing the amount of contact of the conductive filler. As thestrain increases, the conductive resistance increases. The mechanicalproperties, coating geometry (specifically cross-sectional area) andfiller loading level influences the conductive resistance change as wellas hysteresis. Ideally, the polymeric system should be insoluble to anypotential chemicals that it will come in contact with. This polymericsensor only works when the antenna configuration and attachment allowsthe coating to be off the tag as continuous film.

The strain sensor element may also be made directional and therebyprovide an indication of the magnitude and direction of the strain uponthe sensor. In one embodiment, a laminate structure is created wherein afirst layer is as previously described having conductive fillerparticles dispersed within a polymeric matrix. A second layer may beadded to this comprising only a polymeric matrix. A deformation of thelaminate wherein the outer surface of the conductive layer becomesconcave results in a higher conductivity as the spacing betweenconductive particles is reduced. Alternatively, a deformation in theopposite direction wherein the outer surface of the conductive layerbecomes convex yields a greater filler particle spacing and a lowerconductivity.

The tags embodying sensor and communication elements may be used tomonitor an environment by following the steps of: providing a productcomprising an environmentally sensitive sensor system, the sensor systemcomprising: a communications element and a switch configured to enableor disable the communications element, the switch comprising aswitchable polymeric element, the polymeric element having at least afirst electrical state and a second electrical state and beingswitchable between the first and second electrical states as a functionof predefined environmental changes, providing an interrogator adaptedto communicate with the sensor system to determine the state of thecommunication element, exposing the product to potential environmentalchanges, interrogating the state of the communications element of thesensor system. Exemplary interrogators and interrogation include the useof NFC enabled smartphones and appropriate NFC applications to query thecurrent state of a tag placed in an environment of interest.

The elements described herein may be configured into a device comprisinga sensor system. The sensor system in turn comprising: a communicationselement and a switch configured to enable or disable the communicationselement. The switch comprising a switchable polymeric element, thepolymeric element having at least a first electrical state and a secondelectrical state and being switchable between the first and secondelectrical states as a function of predefined environmental changes.

In one embodiment, the device may comprise a consumer product or apackage for a consumer product. The sensor element may be in contactwith a product within the package. The sensor may be disposed within theproduct in a manner and location intended to expose the sensor to aparticular environmental change during the course of use of the productby the consumer. An exemplary use in this manner would include disposinga tag comprising a sensor within a diaper such that insults to thediaper while worn by an infant would produce an environmental changewhich in turn, would alter the electrical state of the sensor elementand the tag as a whole.

Example Sensor Elements:

A humidity-sensitive polyelectrolyte coating with high salt content wasdeveloped as follows. A vial was filled with 10 mL of ultra filtereddeionized water. 1.1688 grams of sodium chloride was added to the vialand mixed with a magnetic stir bar at room temperature until the saltdissolved resulting in a 2 molar salt solution. When the system appearedclear, 0.3 grams of poly(vinyl alcohol) was added. The solution washeated to 90° C. allowing the polymer to go into solution. When thesystem cleared it was ready to be applied to the surface using 10microliter pipette tips with approximately 1-2 millimeters of the tipsremoved. The pipette was set to 5 microliters and the hot polymersolution was applied to the area of interest on the RFID tag. The systemwas then placed into a desiccant chamber and allowed to dry at roomtemperature overnight.

A chemiresistor wetness-sensitive polymer coating was developed asfollows. A vial was filled with 9 mL of ultra filtered deionized water.A separate vial was used to add 0.1 grams of triton X100 to 10milliliters of ultra filtered deionized water for a 1% by weightsolution. 1 milliliter of the 1% by weight Triton X-100 was added to the9 milliliters of ultra-filtered deionized water for a 0.1% by weightTriton X-100 solution. 0.3 grams of poly(vinyl alcohol) was added to the0.1% by weight Triton X-100 solution, add (lower MW and higher %hydrolysis makes the system respond faster than the higher MW and lower% hydrolysis). The solution was heated to 90° C. allowing the polymer togo into solution. When the system cleared, 0.1 grams of the silvercoated copper (AgCU550) conductive filler, available from FerroElectronic Materials Systems, of Mayfield Heights, Ohio, was added. Thesolution was sonicated (degas mode, level 5) for 5 minutes. The systemwas applied to the surface using 10 microliter pipette tips withapproximately 1-2 millimeters of the tips removed. The pipette was setto 5 microliters and the hot polymer solution was applied to the area ofinterest on the RFID tag. The system was then placed into a desiccantchamber and allowed to dry at room temperature overnight.

A second chemiresistor polymer coating designed to respond not to waterbut instead to other environmental chemicals was developed as follows. Avial was filled with 10 mL of Trichloroethylene. 0.6 grams of[poly(ethylene co-vinyl acetate)] was added to the vial. The solution tomix at room temperature until the polymer went into solution. When thesystem was clear, 0.2 grams of the silver coated copper (AgCU550)conductive filler was added. The system was applied to the surface using10 microliter pipette tips with approximately 1-2 millimeters of thetips removed. The pipette was set to 5 microliters and the hot polymersolution was applied to the area of interest on the RFID tag. The systemwas then placed into a fume hood and allowed to dry at room temperatureovernight.

A chemiresistor polymer system designed to respond only to anenvironment having a pH within a target range was developed as follows:The method may use either Talc as the anti-tacking agent and triethylcitrate as the plasticizer or PlasACRYL HTP20 as theanti-tacking/plasticizer. In a 200 mL beaker, 41.7 mL of Eudragit L30D-55, available from Evonik Industries, Essen, Germany, was added to 57mL of deionized water, 14.6 mL of PlasACRYL HTP20, available from EvonikIndustries, and 4.3 grams of the silver coated copper (AgCU550)conductive filler. The solution was mixed with a magnetic stir bar for10 minutes. The solution was used to coat the desired area of the RFtags and cured in a circulating drying oven for 2 hours at 40° C. TheRFID tag turned off when the polymer was exposed to an environmenthaving pH values greater than 5.5.

Additional chemiresistor sensor systems have been designed to respond toan environmental change in pH. It is understood, without being limiting,that polymers, initiators and/or cross-linkers suitable to form a pHsensitive matrix in combination with conductive filler could include orbe a combination of: poly(acrylic acid) (PAA), acrylic acid (AA),2-hydroxyethyl methacrylate (HEMA), poly(hydroxyethylmethacrylate-co-methacrylic acid) (PHEMA-co-MAA), poly(acrylicacid-co-isooctyl acrylate) (poly(AA-co-IOA), poly(acrylamide) (PAAm),poly(methacrylic acid) (PMAA), poly(diethylaminoethyl methacrylate)(PDEAEMA), poly(dimethylaminoethyl methacrylate) (PDMAEMA), poly(vinylalcohol) (PVOH or PVA), poly(ethylene glycol) dimethacrylate (PEGDMA),acrylamide (AAm), N,N-dimethylaminoethyl methacrylate (DMAEMA),N-isopropylacrylamide (NIPAAm), 2-(dimethyl maleinimido) acrylamide(DMIAAm), 2-(dimethyl maleinimido)ethyl methacrylate (DMIMA),poly(2-vinylpyridine) (P2VP), poly(4-vinylpyridine) (P4VP), ethyleneglycol dimethacrylate (EGDMA), glutaraldehyde,azobiz-methylpropionitrile (AIBN), glyoxal, glycerol, cellulosefamilies, any polymer or molecule with alcohol functional groups, anypolymer or molecule with carboxylic acid functional groups.

The model conductive composite system is composed conductive graphitizedcarbon as the conductive filler and a polymer matrix composed ofpoly(vinyl alcohol) and poly(acrylic acid). It is understood that across-linked water-sensitive polymer could be composed of any previouslymentioned polymers but not necessarily sensitive to pH.

Sensing materials may be prepared as follows:

PVOH/PAA/Filler Composite Sensor Element:

Fill two, 150 mL Pyrex glass beakers with 40 mL of deionized water. Adda magnetic stir bar and place beakers on hot/stir plates. Set thestirrers to 400 rpms. Weigh out 3 grams of A99 conductive, graphitized,carbon filler (44 micron diameter) available from Asbury Carbon, and addto each beaker. Allow the stirrer to mix the dry powder into solution.Manually mixing with a spatula can help push any residual powder intosolution. Remove the beakers from hot/stir plates and place in asonication bath and sonicate for 5 minutes to better disperse thefiller. After sonication, place the beakers back onto the hot/stirplates. Set the temperature of the polyvinyl alcohol (PVOH) andpoly(acrylic acid) (PAA) hot/stir plates to 200° C. with stirrers set to400 rpms. Weigh out 4 g of PVOH (89-98K MW, 99% hydrolyzed) and 4 g ofPAA (450K MW), available from Sigma Aldrich, into weigh boats. The PVOHcan be added to the beaker all at once. The PAA needs to be slowly addedto prevent clumping in solution. After each spatula added, enough timeis allowed for the polymer powder on the surface to go into solutionbefore adding the next spatula. Once the polymers are sufficientlydispersed in solution, JKEM thermocouples are added to monitor thetemperature to ensure they stay between 70-80° C. The systems arecovered with paraffin film and allowed to dissolve for three hours.After three hours, the heat is turned off and systems are allowed tocool for 30 minutes while still being stirred. When the temperaturefalls below 30° C., combine PVOH and PAA solutions into a 500 mL beaker.An overhead mechanical mixer is used to handle the higher viscosity andto prevent bubble formation. The two solutions are mixed at roomtemperature for at least two hours at 70 rpms but preferably as long as17 hours control viscosity and prevent filler settling. After mixing,remove any surface bubbles with a disposable pipette. Pour the resultantsolution into a 150×20 mm Petri dish and allow to dry overnight.Alternatively, pour the resultant solution into a syringe to inject overconductive leads to form sensors. After air drying, use a razor blade totrace around the edge of the Petri dish or drying surface and carefullyremove to prevent plastically straining of the polymeric system. Placebetween two silicone sheets and cure at 130° C. for 1 hour. It isunderstood that alternative cure times and temperatures can be used toachieve esterification between the carboxylic acid groups on the PAA andalcohol groups on the PVOH. Remove and allow cooling to room temperaturebefore separating the silicone sheets.

PAA/Glycerol/Filler Composite Sensor Element:

Fill a 150 mL Pyrex glass beaker with 80 mL of deionized water. Add amagnetic stir bar and place beaker on a hot/stir plate. Set the stirrerto 400 rpms. Weigh out 2.4 grams of A99 conductive, graphitized, carbonfiller (44 micron diameter) available from Asbury Carbon, and add to thebeaker. Allow the stirrer to mix the dry powder into solution. Manuallymixing with a spatula can help push any residual powder into solution.Remove the beaker from hot/stir plates and place in a sonication bathand sonicate for 5 minutes to better disperse the filler. Aftersonication, place the beaker back onto the hot/stir plate. Set thetemperature of the hot/stir plate to 200° C. and stirrer to 400 rpms.Weigh out 8 g of PAA (450K MW), available from Sigma Aldrich, into aweigh boat. The PAA needs to be slowly added to prevent clumping insolution. After each spatula added, enough time is allowed for thepolymer powder on the surface to go into solution before adding the nextspatula. Once the polymers are sufficiently dispersed in solution, aJKEM thermocouple is added to monitor the temperature to ensure it staysbetween 50-60° C. and allow the system to dissolve for three hours whilecovered with paraffin film. After three hours, the heat is turned offthe stir plate is allowed to cool. After the solution's temperaturefalls below 30° C., remove from the hotplate to an overhead mechanicalmixer. An overhead mechanical mixer is used to handle the higherviscosity and to prevent bubble formation. Slowly add 0.8 g of glycerol,available from Sigma Aldrich. The two solutions are mixed at roomtemperature for 1 hour at 70 rpms. After mixing, remove any surfacebubbles with a disposable pipette. Pour the resultant solution into a150×20 mm Petri dish and allow to dry overnight. The polymeric systemmay also be incorporated into a mold with conductive leads. After airdrying, use a razor blade to trace around the edge of the Petri dish andcarefully remove to prevent plastically straining of the composite.Place between two silicone sheets and cure at 130° C. for 1 hour. It isunderstood that alternative cure times and temperatures can be used toachieve esterification between the carboxylic acid groups on the PAA andalcohol groups on glycerol. Remove and allow cooling to room temperaturebefore separating the silicone sheets.

PAA/Filler Composite Sensor Element:

Fill a 150 mL Pyrex glass beaker with 80 mL of deionized water. Add amagnetic stir bar and place beaker on a hot/stir plate. Set the stirrerto 400 rpms. Weigh out 2.4 grams of A99 conductive, graphitized, carbonfiller (44 micron diameter) available from Asbury Carbon and add to thebeaker. Allow the stirrer to mix the dry powder into solution. Manuallymixing with a spatula can help push any residual powder into solution.Remove the beaker from hot/stir plates and place in a sonication bathand sonicate for 5 minutes to better disperse the filler. Aftersonication, place the beaker back onto the hot/stir plate. Set thetemperature of the hot/stir plate to 200° C. and stirrer to 400 rpms.Weigh out 8 g of PAA (450K MW), available from Sigma Aldrich, into aweigh boat. The PAA needs to be slowly added to prevent clumping insolution. After each spatula added, enough time is allowed for thepolymer powder on the surface to go into solution before adding the nextspatula. Once the polymer is sufficiently dispersed in solution, a JKEMthermocouple is added to monitor the temperature to ensure it staysbetween 50-60° C. and allow the system to dissolve for three hours anduntil covered with paraffin film. The heat is turned off and the stirplate is allowed to cool for 30 minutes. After mixing, remove anysurface bubbles with a disposable pipette. Pour the resultant solutioninto a 150×20 mm Petri dish and allow to dry overnight. The polymericsystem may also be incorporated into a mold with conductive leads. Afterair drying, use a razor blade to trace around the edge of the Petri dishand carefully remove to prevent plastically straining of the composite.Place between two silicone sheets and cure at 130° C. for 1 hour. It isunderstood that alternative cure times and temperatures can be used toachieve self-crosslinking between the carboxylic acid groups on the PAAto form acid anhydrides. Remove and allow cooling to room temperaturebefore separating the silicone sheets.

Material Preparation:

To dissolve the polymer into an aqueous solution, heat is added to thesystem. The polymers are dissolved in separate beakers and combinedlater to ensure phase separation between the polymer systems does notoccur during the drying process. Even though hydrogen bonding readilyoccurs between the carboxylic acid of the PAA and alcohol of either PVOHor glycerol, above 62° C. free volume effects dominate. To circumventthis, the respective polymer solutions are allowed to cool to roomtemperature while mixing in their respective beakers. Once at roomtemperature, the PAA is added slowly to the crosslinking system (PVOH orglycerol) and allowed to mix for two hours to ensure the two systems arewell dispersed for hydrogen bonding. Longer mixing is done to removewater from the system to increase viscosity to prevent filler fromsettling during the drying process. In practice, the phase separationwas identified with ATR spectra as well as anomalies in the pH sensingdata. A mechanical stirrer is used in the final step to avoid creatingair bubbles in the polymer system.

The pH sensor cross-linking was validated by ATR spectra for esterformation using a Thermo Nicolet Nexus 670 FTIR and several dayexposures to aqueous systems to verify that the system does notdissolve. To acquire dynamic resistance data from the sensor and preventelectrolysis, a power source supplied 1.0 volts and the resultantcurrent was measured by 2831E Measurement (Data Logging Multimeter).Initially, alligator clips were used to attach to the sensing material.The measured current was converted to resistance using Ohm's law. Laterimprovements were made where copper wires were cured into the sensingmaterial to improve measurements and scalability. The weight of thesensor was also recorded to keep track changes as a function of pH.

The pH sensors were tested for dynamic readings while in solution. InpH's 3 and 10, a swelling plateau was reached around 2 minutes withcorresponding resistance changes for the PAA/PVOH version. In pH's 3 and10, a swelling plateau was reached around 1 minute 30 seconds withcorresponding resistance changes for the PAA/Glycerin version. BecausePAA can be readily de-protonated and protonated as a function of pH andtime, a proof-of-concept hysteresis loop test was conducted using asingle sensor with the leading PAA/PVOH system. A weight was recordedfor the sensor before the initial insult starting at pH 4. One hoursubsequent insults and weight changes from de-protonation were recordedfor pH's 5, 5.5, 6, 7, and 9. In an ideal system, the reversing of thesame pH insults would cause the new volume to shrink back to therespective volumes. However, volume shrinkage undergoes hysteresis dueto protonating time constants, pH distance from the pKa value,irreversible changes to the strain network from some broken acidanhydride and PAA/PVOH ester bonds create a hysteresis. This hysteresiscan be correlated to insult time and environmental pH and ultimately anelectrical resistance value. Once the pH falls to the pKa of thepolymer, the protonation will plateau.

A polymeric system sensitive to mechanical strain was developed bysubstituting an elastic polymer for the environmentally sensitivepolymer as follows: 8 grams of silicone RTV rubber was mixed with 8grams of conductive filler in a beaker to obtain a 50/50 ratio ofpolymer. The mixture was extruded through a plastic 20 mL syringe. Thestrips were extruded onto a silicone surface for easy removal. In oneembodiment, an additional layer of the silicone was extruded upon thesilicone conductive filler layer and allowed to cure. The roomtemperature vulcanization was allowed to proceed for 24 hours. Thestrain sensor strip was removed and tested for dynamic conductivity andmechanical properties (Young's modulus, elastic region, Yield point).The Instron was set to constant extension at 1 mm/sec until break. Theresistance was measured in parallel with a 2831E Measurement (DataLogging Multimeter) and small alligator clips attached to the sample.The Young's modulus was calculated with the Instron software. Asecondary test was conducted without alligator clips where the finalstrain of 150% strain from extension where the break occurred in themiddle of the strain sensor.

The exemplary tag systems demonstrate the incorporation of the sensorelements and the communication elements. The sensor elements may also becreated as standalone devices for use in any system where anelectrically switchable sensor for the described environmental changesis desired.

A polymeric system sensitive to directional strain was developed bytailoring the viscosity of a polymer system such that filler will settlewith gravity to result in a pre-determined non-conductive to conductivecontinuum in the matrix. With this filler loading level continuum,directional strain may be identified with a drop in resistance as thesystem is bent toward the conductive side or an increase in resistanceas it is bent toward the non-conductive side. The polymer system may bethermoset, thermoplastic, or elastomer in nature. Suitable polymerfamilies are esters, amides, urethanes, silicones, epoxy resins, ethers,ethylene, and vinyls to name a few. Conductive filler can be metallic ornon-metallic. In our case, a model system was designed withnon-metallic, conductive graphitized carbon filler and a polymer matrixcomposed of poly(vinyl alcohol) and poly(acrylic acid).

PAA/PVOH/Filler Directional Strain Sensor Composite:

Fill two, 150 mL Pyrex glass beakers with 40 mL of deionized water. Adda magnetic stir bar and place beakers on hot/stir plates. Set thestirrers to 400 rpms. Weigh out 1.2 grams of A99 conductive,graphitized, carbon filler (44 micron diameter) available from AsburyCarbon, and add to each beaker. Allow the stirrer to mix the dry powderinto solution. Manually mixing with a spatula can help push any residualpowder into solution. Remove the beakers from hot/stir plates and placein a sonication bath and sonicate for 5 minutes to better disperse thefiller. After sonication, place the beakers back onto the hot/stirplates. Set the temperature of the polyvinyl alcohol (PVOH) andpoly(acrylic acid) (PAA) hot/stir plates to 200° C. with stirrers set to400 rpms. Weigh out 4 g of PVOH (89-98K MW, 99% hydrolyzed) and 4 g ofPAA (450K MW), available from Sigma Aldrich, into weigh boats. The PVOHcan be added to the beaker all at once. The PAA needs to be slowly addedto prevent clumping in solution. After each spatula added, enough timeis allowed for the polymer powder on the surface to go into solutionbefore adding the next spatula. Once the polymers are sufficientlydispersed in solution, JKEM thermocouples are added to monitor thetemperature to ensure they stay between 70-80° C. The systems arecovered with paraffin film and allowed to dissolve for three hours.After three hours, the heat is turned off and systems are allowed tocool for 30 minutes while still being stirred. When the temperaturefalls below 30° C., combine PVOH and PAA solutions into a 500 mL beaker.An overhead mechanical mixer is used to handle the higher viscosity andto prevent bubble formation. The two solutions are mixed at roomtemperature for at least two hours at 70 to mix thoroughly but maintainwater content for low viscosity to enable the filler to settle into acontinuum. After mixing, remove any surface bubbles with a disposablepipette. Pour the resultant solution into a 150×20 mm Petri dish andallow to dry overnight. After air drying, use a razor blade to tracearound the edge of the Petri dish or drying surface and carefully removeto prevent plastically straining of the polymeric system. Place betweentwo silicone sheets and cure at 130° C. for 1 hour. It is understoodthat alternative cure times and temperatures can be used to achieveesterification between the carboxylic acid groups on the PAA and alcoholgroups on the PVOH. Remove and allow cooling to room temperature beforeseparating the silicone sheets. Strips of material were cut in 1 cm by 4cm strips and clamped with alligator clips at the ends. A flukemultimeter was used to acquire resistance changes. The equilibriumresistance was about 490 ohms As the sensor was bent toward theconductive side, the resistance lowered to 336 ohms due to compressionof conductive filler. As the sensor was bent toward the non-conductiveside, the resistance increased to 618 ohms due to slipping andseparation of conductive filler pathways. After releasing the strain,the sensor returned back to its equilibrium value of about 490 ohms.

As shown in FIG. 1, a sensor element 1000 includes a polymeric matrix100 and conductive filler elements 200, embedded in the matrix. As shownin FIG. 2, the sensor element 1000 comprises a polymeric matrix 100,conductive filler 200 and a layer of unfilled matrix 300.

In one aspect, the sensor system comprises a tag. The tag may compriseone or more layers of conductive inks and non-conductive inks printedupon a substrate. Exemplary substrate materials include: polymer films,paper, high permittivity dielectric materials, and FR-4 material.Multiple layer structures may further comprise partial layers ofnon-conducting material separating at least portions of the conductivelayers. Exemplary conductive layers include copper and silver inks. Thetag comprises at least one sensor, a radio-frequency chip, and a firstantenna disposed as a circuit upon a card, coin, or inlay. The chip maybe active or passive. Exemplary chip/first antenna combinations includemodel numbers: RI-I03-112A-03 (13.56 MHz), and RI-INL-R9QM (134.2 kHz),or model TRF7970A, each available from Texas Instruments, Dallas, Tex.The antenna may be in the physical form of a coil or a dipole, or aconductive component of a product or package in electrical communicationwith the remainder of the tag.

The needed power supply for the sensors may be provided by the harvestedenergy of the RFID circuit because the needed current is in the microampere range. The harvested power may be stored with an element such asa capacitor for use by the sensor at a later time.

The tag may be configured such that the output of the sensor alters thevalue of one or more bits of the word stored in the memory of the tag'schip. In one embodiment, any non-zero sensor output may alter adesignated bit's value either from one to zero or from zero to one.Alternatively, the tag's circuit may provide a bias against which thesensor output is compared. In this embodiment, only sensor outputs abovethe bias threshold, or between a lower and upper set of thresholds mayalter the bit's value.

The tag may comprise more than a single sensor. In one configuration ofa multi sensor tag, each sensor's output may be used to alter the valueof its own respective bit. In an alternative configuration, the set ofsensors may be polled when the tag is powered such that a singleparticular bit of the tag's memory is stepped through a series of valuesdepending upon the output of each polled sensor. As noted before, thetag may be designed such that any non-zero sensor output will alter thevalue of the associated bit, or such that only values above a lowerthreshold, or between an upper and lower threshold will alter therespective bit value.

The tag may be read using a radio frequency protocol such as the NearField Communications (NFC) protocol. When the tag is interrogated, orread, the tag circuit is powered, the sensor output alters the memory ofthe tag. The memory of the tag is then read by an interrogator. Theacquires a digital value of the memory word indicative of the sensedstate of the environment of the tag. The relevant communicationsfrequency range of the tag may be HF, UHF or other appropriatelyselected frequency ranges as determined by the specific need of the tagin terms of the intended environment and uses of the tag.

The sensor system may further comprise an interrogator. The interrogatorcomprising a power source and a second antenna adapted to generateelectromagnetic radiation comprising a resonant frequency of the firstantenna, and a receiver adapted to detect electromagnetic radiation andde-modulate the detected radiation extracting embedded data from thedetected radiation. The Bluetooth™ RFID Reader, model number 223012,available GAO RFID, of Toronto Canada, exemplifies one form ofinterrogator. The model 223012 interrogator has the capacity tointerrogate the radio frequency tag and to determine the state of thememory of the tag and thus extract information associated with theoutput of the sensor or sensors relating to the environment of the tag.The 223012 further comprises a secondary network communications linkutilizing the Bluetooth™ communications protocol for transmitting theinformation extracted from the tag to a secondary device or secondaryinterrogator, such as a Bluetooth™ enabled computer or smart phone. Thesecondary interrogator may further analyze the information relating tothe state of the tag and/or the tags environment and provide an outputassociated with a particular tag and/or tag environment state. Theinterrogator may further comprise a display element such as an LCD orLED screen for displaying an output associated with the analyzed taginformation. The interrogator may further comprise one or more sensorsfor ascertaining information associated with the environment of theinterrogator. The sensors may include: temperature, humidity,acceleration sensors. The interrogator may further comprise one or morecameras enabling the capture of images associated with a product, thetag or the environment. The interrogator may comprise a GlobalPositioning capability enabling the interrogator to ascertain and shareinformation relating to the geographic location of the interrogator.

In one aspect, the Smartphone may serve as the only interrogator. Inthis aspect the smart phone may interrogate the tag thereby ascertainingthe information from the memory of the tag. The interrogator may analyzeor otherwise interpret the information and may create an output. Theoutput may be provided to a system user via an audio output, visualoutput, haptic output or combinations thereof. The interrogator mayutilize inputs from sensors or systems of the smart phone, includinginformation and analysis available from a networked resource such ascloud computing resources, in addition to the tag information increating the output. Exemplary smart phones suitably configured toperform as a system interrogator include: the Ace™ E320 Liquid Express,the Blackberry™ Bole 970, available from Research In Motion of; theCasio IT-800; the Google Nexus 7™, available from Google, Inc. MountainView Ca.; the HTC Desire C™, available from HTC of; the LG OptimusElite; the Motorola Droid™ Razr™, available from Motorola; the Nokia700; the Panasonic BizPad™; and the Samsung Galaxy S Advance™.

In one aspect, the sensor system may include a product. The term“product(s)” is used in the broadest sense and refers to any product,product group, services, communications, entertainment, environments,organizations, systems, tools, and the like. For example, an example ofa product group is personal and household products, such as used by aperson, family or household. Examples of a representative, andnon-limiting list of product categories within the personal andhousehold product group includes antiperspirants, baby care, colognes,commercial products (including wholesale, industrial, and commercialmarket analogs to consumer-oriented consumer products), cosmetics,deodorants, dish care, feminine protection, hair care, hair color,health care, household cleaners, laundry, oral care, paper products,personal cleansing, disposable absorbent articles, pet health andnutrition, prescription drugs, prestige fragrances, skin care, foods,snacks and beverages, special fabric care, shaving and other hair growthmanagement products, small appliances, devices and batteries, servicessuch as haircutting, beauty treatment, spa treatment, medical, dental,vision services, entertainment venues such as theaters, stadiums, aswell as entertainment services such as film or movie shows, plays andsporting events A variety of product forms may fall within each of theseproduct categories.

Exemplary product forms and brands are described on The Procter & GambleCompany's website www.pg.com, and the linked sites found thereon. It isto be understood that consumer products that are part of productcategories other than those listed above are also contemplated by thepresent invention, and that alternative product forms and brands otherthan those disclosed on the above-identified website are alsoencompassed by the present invention.

Other product groups include but are not limited to: sports equipment,entertainment (books, movies, music, etc), vision, and in-home-consumedmedical and first aid, among others.

The tag may be attached to the packaging of the product such as theprimary packaging of a liquid product, or a granular product. The tagmay be immersed in or float upon the surface of a packaged liquid orgranular product. The tag may be incorporated within the product such aswithin a disposable absorbent article such as within a diaper for thepurpose of detecting an insult to the absorbent core of the diaper. Thetag may be disposed upon the surface of the product itself such as uponthe surface of a battery for the purpose of sensing information relatingto the useful power remaining in the battery.

It is believed that conforming the antenna of the tag to the shape ofthe outer surface of the product yields a system where communicationbetween the interrogator and the tag may be omni-directional orachievable at a variety of angles between the interrogator and the tag.

One of the problems associated with creating a communication device forvarious products is realized when the communication device is utilizedon electromagnetically conductive bodies. Free space radio propagationprinciples do not apply near highly conductive bodies. Additionally,antenna performance is severely degraded when antennas are placed nearmetals. As such, simply placing an RFID tag on a battery or on an objectwith a conductive body may not accomplish the desired effect, e.g. powerharvesting and/or data transfer. Notably, this problem is not limited torechargeable/disposable batteries. For example, a can of shaving gel,foam, etc., or a package comprising a metalized film, could experiencethe same issues because of the conductivity of the container. Ingeneral, an RFID tag next to metallic body decreases signal couplingbetween the reader and the tag by 10×.

One way to prevent the effects arising from metal proximity to theantenna is to prevent the electromagnetic field from entering the metal.For example, separating the antenna and the metal surface by placing amaterial with suitable electromagnetic properties and dimensions betweenthem may divert the electromagnetic field around the metallic/conductivebody of the product. The properties of the diverter material depend onthe exact metal used and the RFID frequency. The magnetic divertereffectively isolates the tag from the can. An effective separation mayalso be achieved with an air filled gap between the materials.

In one aspect, a method of determining product information comprisessteps of: providing a product comprising a tag as described above. Thetag comprising, at least one sensor adapted to provide an outputanalogous to a change in an environment of the sensor. The sensor havingat least one output terminal. The tag also includes a radio-frequencychip comprising a memory element, input terminal(s) and outputterminal(s), the input terminal(s) disposed in electrical communicationwith the output terminals of the sensor, and a first antenna disposed inelectrical communication with the output terminals of the chip.

The method may also include providing an interrogator adapted to detectradiation associated with the data of the tag. The interrogator may bean RF or NFC protocol reader coupled with a Bluetooth™ capability asdescribed above, or a smart phone or other computing device comprisingan RF or NFC capable reader.

In one aspect the method may be minimized to providing productsincluding tags and providing software compatible with devices availablein the market or in the possession of consumers. A consumer may chooseto avail themselves of the application software which will enable theirdevice to functions as the described interrogator.

The interrogator may be used to determine the current state of the tagutilizing an RF communications protocol such as the NFC protocol. Theinterrogator may interpret the data received from the tag using asoftware application written for that purpose.

In one aspect, the interrogator may incorporate a secondary networkcommunication module affording the device an ability to send and receivedata over a cellular phone or other networks including a local area orwifi networks. In such an aspect, the interrogator may transmit datareceived from the tag and/or an analysis of the data from the tag. Thesoftware application of the interrogator may analyze the data from thetag to determine if replenishment of the product associated with the tagin needed, or to project when such replenishment will be needed in viewof usage history of the product established via a series ofinterrogations of the tag. In this aspect the application may be used toconsummate a purchase of addition product via the network. Theapplication may be further utilized to offer the user related productsfor purchase, or to make offers of other products not directly relatedto the product.

In one embodiment, the system tag may be subdivided into portions. Oneportion may contain the antenna and the chip, the other portion maycontain the sensor. The two portions of the tag may be disposed with thesensor exposed to the functional environment of an absorbent article,and the antenna and chip portion removed from exposure to the functionalenvironment of the article. The antenna and chip portion may be maderemovable and therefore reusable as well. In one embodiment, conductivehook and loop fasteners, such as are available from APLIX Inc., ofCharlotte, N.C., may be used to create an interface between thefunctional environment of the article and the exterior of the article.The attachment mechanism between the article, sensor and the removabletag to enable conductivity can be hook & loop, compression (e.g. elasticband, garter), adhesion (e.g. adhesive strip), magnetic, or combinationsthereof. In this embodiment, the sensor may be fabricated as an assemblyin electrical contact with the conductive hook and loop pads which inturn are disposed upon an exterior surface of the article while thesensor may be disposed within the article in the functional environment.Matching pads may be incorporated as part of the assembly of the antennaand chip assembly and the two respective assemblies may be united usingthe matching hook and loop pads for operational use of the tag. In thismanner, the more costly antenna and chip assembly may be renderedreusable thereby reducing the overall cost associated with using thesystem with a number of respective disposable articles. The respectiveassemblies may be formed using conductive adhesive, such as is availablefrom MG Chemicals, of Surrey, B.C., Canada to affix the electrical leadsof the respective portions of the tags to their respective hook and loopfastener pads.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm” Every document cited herein, including any crossreferenced or related patent or application and any patent applicationor patent to which this application claims priority or benefit thereof,is hereby incorporated herein by reference in its entirety unlessexpressly excluded or otherwise limited. The citation of any document isnot an admission that it is prior art with respect to any inventiondisclosed or claimed herein or that it alone, or in any combination withany other reference or references, teaches, suggests or discloses anysuch invention. Further, to the extent that any meaning or definition ofa term in this document conflicts with any meaning or definition of thesame term in a document incorporated by reference, the meaning ordefinition assigned to that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A sensor system comprising: a switchablepolymeric element, the polymeric element has at least a first electricalstate and a second electrical state and is switchable between the firstand second electrical states as a function of predefined environmentalchanges, the sensor comprises a polymeric matrix and a plurality ofconductive particles embedded in the polymeric matrix.
 2. The sensoraccording to claim 1 wherein the polymer comprises polyvinyl alcohol. 3.The sensor according to claim 1 wherein the conductive particlescomprise silver coated copper particles.
 4. The sensor according toclaim 1 wherein the conductive particles comprise carbon particles. 5.The sensor according to claim 1 further comprising a surfactant.
 6. Asensor system comprising: a switchable polymeric element, the polymericelement has at least a first electrical state, a second electricalstate, and a third electrical state and is switchable between the first,second, and third electrical states as a function of predefinedenvironmental changes associated with moisture, the sensor comprises apolymeric matrix and a plurality of conductive particles embedded in thepolymeric matrix.
 7. The sensor according to claim 6 wherein the polymercomprises polyvinyl alcohol.
 8. The sensor according to claim 6 whereinthe conductive particles comprise silver coated copper particles.
 9. Thesensor according to claim 6 wherein the conductive particles comprisecarbon particles.
 10. The sensor according to claim 6 further comprisinga surfactant.